US20230268552A1 - Electrolyte for lithium battery, and lithium battery comprising same - Google Patents
Electrolyte for lithium battery, and lithium battery comprising same Download PDFInfo
- Publication number
- US20230268552A1 US20230268552A1 US18/003,717 US202118003717A US2023268552A1 US 20230268552 A1 US20230268552 A1 US 20230268552A1 US 202118003717 A US202118003717 A US 202118003717A US 2023268552 A1 US2023268552 A1 US 2023268552A1
- Authority
- US
- United States
- Prior art keywords
- group
- substituted
- electrolyte
- unsubstituted
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 90
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 88
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 150000001875 compounds Chemical class 0.000 claims abstract description 99
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 25
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims description 31
- 239000007774 positive electrode material Substances 0.000 claims description 23
- 239000007773 negative electrode material Substances 0.000 claims description 22
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- -1 pentafluoroethanesulfonyl group Chemical group 0.000 claims description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 15
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 15
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 13
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 13
- 150000008053 sultones Chemical class 0.000 claims description 13
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 12
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 12
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 11
- 150000004767 nitrides Chemical class 0.000 claims description 11
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 10
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 10
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 6
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical group O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910021481 rutherfordium Inorganic materials 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004492 methyl ester group Chemical group 0.000 claims description 3
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 239000011572 manganese Substances 0.000 description 16
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000004020 conductor Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 239000007784 solid electrolyte Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- 229910008557 LiaNi1-b-cCob Inorganic materials 0.000 description 5
- 229910014968 LiaNi1−b−cCob Inorganic materials 0.000 description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011856 silicon-based particle Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 229910014638 LiaNib Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 230000016507 interphase Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910021382 natural graphite Inorganic materials 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 229910008583 LiaNi1-b-cMnb Inorganic materials 0.000 description 3
- 229910014615 LiaNi1−b−cMnb Inorganic materials 0.000 description 3
- 229910014601 LiaNi1−b−cMnbB Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 206010011416 Croup infectious Diseases 0.000 description 2
- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 description 2
- 229910001559 LiC4F9SO3 Inorganic materials 0.000 description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 2
- 229910021447 LiN(CxF2x+1SO2)(CyF2y+1SO2) Inorganic materials 0.000 description 2
- 229910013124 LiNiVO4 Inorganic materials 0.000 description 2
- 229910012946 LiV2O5 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910021475 bohrium Inorganic materials 0.000 description 2
- 229910052795 boron group element Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229910052800 carbon group element Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 201000010549 croup Diseases 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229910021473 hassium Inorganic materials 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006051 mesophase pitch carbide Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052699 polonium Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910021477 seaborgium Inorganic materials 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 229910052713 technetium Inorganic materials 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910014455 Ca-Cb Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013298 LiMS2 Inorganic materials 0.000 description 1
- 229910021466 LiQS2 Inorganic materials 0.000 description 1
- 229910021462 LiaCoGbO2 Inorganic materials 0.000 description 1
- 229910008676 LiaMn2 Inorganic materials 0.000 description 1
- 229910021464 LiaMn2GbO4 Inorganic materials 0.000 description 1
- 229910008694 LiaMn2O4 Inorganic materials 0.000 description 1
- 229910021461 LiaNiGbO2 Inorganic materials 0.000 description 1
- 229910021460 LiaNibCocMndGeO2 Inorganic materials 0.000 description 1
- 229910021459 LiaNibEcGdO2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910008326 Si-Y Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006773 Si—Y Inorganic materials 0.000 description 1
- 229910020997 Sn-Y Inorganic materials 0.000 description 1
- 229910008859 Sn—Y Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229910021479 dubnium Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001326 naphthylalkyl group Chemical group 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical compound [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- YGPLJIIQQIDVFJ-UHFFFAOYSA-N rutherfordium atom Chemical compound [Rf] YGPLJIIQQIDVFJ-UHFFFAOYSA-N 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BFDWBSRJQZPEEB-UHFFFAOYSA-L sodium fluorophosphate Chemical compound [Na+].[Na+].[O-]P([O-])(F)=O BFDWBSRJQZPEEB-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- PRZWBGYJMNFKBT-UHFFFAOYSA-N yttrium Chemical compound [Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y] PRZWBGYJMNFKBT-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/0042—Four or more solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to an electrolyte for a lithium battery and a lithium battery including the same.
- Lithium batteries have energy density per unit weight that is three times higher than that of a lead-acid battery, a nickel-cadmium battery, a nickel-hydrogen battery, a nickel-zinc battery, and the like in the art, and can be charged at high speed.
- an organic electrolyte solution is generally in a lithium secondary battery.
- the organic electrolyte solution is prepared by dissolving a lithium salt in a non-aqueous organic solvent.
- a material stable at a high voltage and having high ionic conductivity and dielectric permittivity and low viscosity is preferable.
- organic electrolyte solution as an electrolyte for a lithium secondary battery may cause degradation in capacity and lifespan characteristics of the lithium secondary battery due to side reactions between an electrolyte and a negative electrode/positive electrode.
- additives used in the electrolyte for a lithium secondary battery are used in order to compensate for this point.
- additives used so far do not provide sufficient capacity and lifespan characteristics of a battery over a wide temperature range between a low temperature below zero and a high temperature.
- an electrolyte for a lithium battery and a lithium battery including the same capable of providing sufficient capacity and lifespan characteristics of a battery over a wide temperature range between a low temperature below zero and a high temperature.
- One aspect is to provide an electrolyte for a lithium battery, including a novel electrolyte additive.
- Another aspect is to provide a lithium battery including the electrolyte.
- an electrolyte for a lithium battery includes:
- Y may be a halogen atom or a substituted or unsubstituted C1-C1O alkoxy group
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may each independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C6-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group.
- the compound represented by Formula 1 may be represented by Formula 2:
- Y′ may be a halogen atom or a substituted or unsubstituted C1-C10 alkoxy group
- R′ 1 , R′ 2 , R′ 3 , R′ 4 , R′ 5 , and R′ 6 may each independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C6-C50 alkylaryl group.
- the compound represented by Formula 1 may be represented by Formula 3:
- Y′′ may be a halogen atom
- R a , R b , R c , R d , and R f may each independently be an unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group substituted with a halogen atom, an unsubstituted C2-C10 alkenyl group, a C2-C10 alkenyl group substituted with a halogen atom, an unsubstituted C6-C50 alkylaryl group, or a C6-C50 alkylaryl group substituted with a halogen atom.
- the compound represented by Formula 1 may be represented by Formulae 4 to
- the amount of the additive may be in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte.
- the electrolyte may further include a cyclic carbonate-based compound, and
- the cyclic carbonate-based compound may be selected from: fluoroethylene carbonate (FEC); FFC substituted with at least one substituent selected from a halogen atom, a cyano group (CN), and a nitro group (NO 2 ); vinyl ethylene carbonate (VEC); VEC substituted with at least one substituent selected from a halogen atom, CN, and NO 2 ; vinylene carbonate (VC); and VC substituted with at least one substituent selected from a halogen atom, CN, and NO 2 .
- FEC fluoroethylene carbonate
- FFC fluoroethylene carbonate
- VEC vinyl ethylene carbonate
- VEC VEC substituted with at least one substituent selected from a halogen atom, CN, and NO 2
- vinylene carbonate (VC) and VC substituted with at least one substituent selected from a halogen atom, CN, and NO 2 .
- the electrolyte may further include at least one selected from a sultone-based compound, a nitride-based compound, and a cyanide-based compound.
- the sultone-based compound may be: sultone; or propane sultone substituted with at least one substituent selected from a halogen atom, a cyano group, a nitro group, a trifluoromethanesulfonic group, a pentafluoroethanesulfonyl group (SO 2 C 2 F 5 ), a pentafluorophenyl group (C 6 F 5 ), a methanesulfonyl group (SO 2 CF 3 ), a phenylsulfonyl group (SO 2 Ph), and a methylester group (COOCH 3 ).
- the nitride-based compound may be succinonitrile
- the cyanide-based compound may be 1,3,6-hexane tri-cyanide (HTCN) or 1,2,6-(HTCN).
- the amount of the sultone-based compound, the nitride-based compound, or the cyanide-based compound may be in a range of 0.01 wt % to 5 wt % based on the total weight of the electrolyte.
- the lithium salt may include at least one selected from LiPF 6 , LiBF 4 , LiSbF 6 , LiASF 6 , LiClO 4 , LiCF 3 SO3, Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 )(where and 2 ⁇ x ⁇ 20 and 2 ⁇ y ⁇ 20), LiCl, and Lil.
- the non-aqueous organic solvent may include at least one selected from ethylene carbonate (EC), propylene carbonate (PC), ethylmethyl carbonate (EMC), methylpropyl carbonate, ethylpropyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, vinylethylene carbonate (VEC), butylene carbonate, ethyl propionate (EP), propyl propionate (PP), ethyl butylate, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, gamma-valerolactone, gamma-butyrolactone, and tetrahydrofuran.
- EC ethylene carbonate
- PC propylene carbonate
- EMC ethylmethyl carbonate
- DMC dimethyl carbonate
- DEC diethyl carbonate
- VEC vinylethylene carbonate
- EP ethyl propionate
- PP propyl prop
- a lithium battery includes:
- the negative electrode active material may include a carbon-based material, a silicon-based material, or a silicon-carbon-based composite.
- the negative electrode active material may include amorphous, plate-like, flake-like, spherical, or fibrous graphite, such as natural graphite or artificial graphite.
- the lithium battery may further include a separator between the positive electrode and the negative electrode.
- the electrolyte for a lithium battery includes an additive including a compound represented by Formula 1.
- a lithium battery including the electrolyte may have improved discharge capacity (ratio) and lifespan characteristics at a low temperature ( ⁇ 10° C.) below zero and a high temperature (45° C.).
- FIG. 1 is a schematic view of a lithium battery according to an embodiment.
- a combination thereof means a mixture or combination of one or more of the aforementioned elements.
- An electrolyte for a lithium battery may include: a lithium salt; a non-aqueous organic solvent; and an additive including a compound represented by Formula 1:
- X 1 and X 2 may each independently be —O— or —N—;
- Y may be a halogen atom or a substituted or unsubstituted C1-C10 alkoxy group
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may each independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C6-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group.
- the electrolyte for a lithium battery may include, as an additive, the compound represented by Formula 1.
- the compound may be an additive having a symmetric structure in which silyl groups are located on both sides of a center at which a phosphorus (P) element and an oxygen (O) element form a double bond (—P ⁇ O).
- a lithium battery using the electrolyte that includes the additive may have improved discharge capacity (ratio) and lifespan characteristics at a low temperature ( ⁇ 10° C.) below zero and a high temperature (45° C.).
- a cathode electrolyte interphase (CEI) film may be formed on a surface of a positive electrode.
- the CEI film strongly interacts with metal ions of a metal oxide included in a positive electrode active material so that the reaction center at the interface between the electrolyte and a positive electrode can be completely capped to be deactivated.
- the CEI film may prevent generation of by-products, such as gas or/and HF, by preventing oxidation of a solvent included in the electrolyte, and may also prevent the elusion of metal ions of a metal oxide included in a positive electrode active material.
- the lithium battery including the electrolyte, resistance at the interface between the electrolyte and a positive electrode is lowered so that lithium ion conductivity may be improved while a low-temperature discharge voltage may increase. As a result, the lithium battery may have improved cycle stability and rate performance.
- the additive may have a symmetric structure in which silyl groups are located on both sides of a center at which a phosphorus (P) element and an oxygen (O) element form a double bond (—P ⁇ O).
- Such an additive may have a high concentration of silyl groups compared to an additive having a structure in which a silyl group is located only on one side.
- SEI solid electrolyte interphase
- the compound represented by Formula 1 may include a compound represented by Formula 2:
- Y′ may be a halogen atom or a substituted or unsubstituted C1-C16 alkoxy group
- R′ 1 , R′ 2 , R′ 3 , R′ 4 , R′ 5 , and R′ 6 may each independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C6-C50 alkylaryl group.
- the compound represented by Formula 1 may include a compound represented by Formula 3:
- Y′′ may be a halogen atom
- R a , R b , R c , R d , R e , and R f may each independently be an unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group substituted with a halogen atom, an unsubstituted C2-C10 alkenyl group, a C2-C10 alkenyl group substituted with a halogen atom, an unsubstituted C6-C50 alkylaryl group, or a C6-C50 alkylaryl group substituted with a halogen atom.
- the compound represented by Formula 1 may include a compound represented by Formulae 4 to 12:
- the amount of the additive may be in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte.
- the amount of the additive may be, based on the total weight of the electrolyte, in a range of 0.01 wt % to 9 wt %, 0.01 wt % to 8 wt %, 0.01 wt % to 7 wt %, 0.01 wt % to 6 wt %, 0.01 wt % to 5 wt %, 0.01 wt % to 4 wt %, 0.01 wt % to 3 wt %, or 0.01 wt % to 2 wt %.
- the lithium battery may have improved discharge capacity (ratio) and lifespan characteristics at a low temperature ( ⁇ 10° C.) below zero and a high temperature (45° C.).
- the electrolyte may further include a cyclic carbonate-based compound, and the cyclic carbonate-based compound may be selected from: fluoroethylene carbonate (FEC); FEC substituted with at least one substituent selected from a halogen atom, a cyano group (CN), and a nitro group (NO 2 ); vinylethylene carbonate (VEC); VEC substituted with at least one substituent selected from a halogen atom, CN, and NO 2 ; vinylene carbonate (VC); and VC substituted with at least one substituent selected from a halogen atom, CN, and NO 2 .
- FEC fluoroethylene carbonate
- FEC fluoroethylene carbonate
- VEC vinylethylene carbonate
- VEC VEC substituted with at least one substituent selected from a halogen atom, CN, and NO 2
- VC vinylene carbonate
- VC VC substituted with at least one substituent selected from a halogen
- the amount of the cyclic carbonate-based compound may be in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte.
- the amount of the cyclic carbonate-based compound may be in a range of 0.1 wt % to 10 wt % or 0.5 wt % to 10 wt %, based on the total weight of the electrolyte.
- An SEI film formed by a reaction between the cyclic carbonate-based compound and either of a negative electrode active material or a negative electrode surface may have more flexible characteristics. Accordingly, the lifespan characteristics of the lithium battery may be further improved.
- the electrolyte may further include at least one selected from a sultone-based compound, a nitride-based compound, and a cyanide-based compound, wherein the sultone-based compound may include: propane sultone; or propane sultone substituted at least one substituent selected from a halogen atom, a cyano group, a nitro group, a trifluoromethane sulfonyl group, a pentafluoroethane sulfonyl group (SO 2 C 2 F 5 ), a pentafluorophenyl group (C 6 F 5 ), a methane sulfonyl group (SO 2 CF 3 ), a phenyl sulfonyl group (SO 2 Ph), and a methyl ester group(COOCH 3 ), the nitride-based compound may include succinonitrile, and the cyanide-based compound may include 1, 3, 6-hexane tri-
- the amount of the sultone-based compound, the nitride-based compound, or the cyanide-based compound may be in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte.
- the amount of the sultone-based compound, the nitride-based compound, or the cyanide-based compound may be in a range of 0.1 wt % to 10 wt %, 0.5 wt % to 10 wt %, or 1 wt % to 10 wt %, based on the total weight of the electrolyte,
- the sultone-based compound orland the nitride-based compound is further added to the electrolyte
- the interfacial resistance of a negative electrode may be lowered and the thermal stability is improved, and thus the lifespan characteristics of lithium battery at a high temperature may be further improved.
- the cyanide-based compound is further added to the electrolyte, the thickness of the lithium battery may be reduced, and accordingly, the stability of the battery against thermal shock may be improved.
- the lithium salt may include at least one selected from LiPF 6 , LiBF 4 , LiSbF 6 , LiASF 6 , LiClO 4 , LiCF 3 SO3, Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 )(where and 2 ⁇ x ⁇ 20 and 2 ⁇ y ⁇ 20), LiCl, and Lil.
- the concentration of the lithium salt may be in a range of 0.01 M to 2.0 M, but is not necessarily limited thereto. An appropriate concentration may be used as needed. Within the concentration ranges above, the battery performance may be further improved.
- the non-aqueous organic solvent may include at least one selected from ethylene carbonate (EC), propylene carbonate (PC), ethylmethyl carbonate (EMC), methylpropyl carbonate, ethylpropyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, vinylethylene carbonate (VEC), butylene carbonate, ethyl propionate (EP), propyl propionate (PP), ethyl butylate, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, gamma-valerolactone, gamma-butyrolactone, and tetrahydrofuran.
- EC ethylene carbonate
- PC propylene carbonate
- EMC ethylmethyl carbonate
- DMC diethyl carbonate
- VEC vinylethylene carbonate
- EP ethyl propionate
- PP propyl propionate
- the electrolyte may be in a liquid state or a gel state.
- a lithium battery according to another embodiment may include: a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; and the electrolyte disposed between the positive electrode and the negative electrode.
- the shape of the lithium battery is not particularly limited, and the lithium battery, such as a lithium ion battery, a lithium ion polymer battery, a lithium sulfur battery, and the like, may also include a lithium primary battery.
- the lithium battery may have improved discharge capacity (ratio) and lifespan characteristics at a low temperature ( ⁇ 10° C.) below zero and a high temperature (45° C.).
- the positive electrode active material may be selected from compounds represented by the following formulae: Li b A 1-b D′ b E 2 (where 0.90 ⁇ a ⁇ 1.8 and 0 ⁇ b ⁇ 0 . 5 ); Li a G 1-b D′ b O 2-c E c (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiG 2-b D′ b O 4-c E c (where 0 ⁇ b ⁇ 0.5 and 0 ⁇ c ⁇ 0.05); Li a Ni 1-b-c Co b D′ c E ⁇ (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-b-c Co b D′ c O2- ⁇ J ⁇ (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5.
- Li a Ni 1-b-c Co b D′ c O2- ⁇ J 2 (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2)
- Li a Ni 1-b-c Mn b D′ c E ⁇ (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2)
- Li a Ni 1-b-c Mn b D′ c O2- ⁇ J ⁇ (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2)
- Li a Ni 1-b-c Mn b D′ c O2- ⁇ J 2 (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2)
- Li a Ni b G c L d O2 (where 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.9, 0 ⁇ c ⁇ 0.5, and 0.0001 ⁇
- Li a MnL b O 2 (where 0.90 ⁇ a ⁇ 1.8 and 0.001 ⁇ b ⁇ 0.2); Li a Mn 2 L b O 4 a ⁇ 1.8 and a ⁇ 1.8 and 0.001 ⁇ b ⁇ 0.2); Li a Mn 2 O 4 (where 0.90 ⁇ a ⁇ 1.8); MO 2 ; MS 2 ; LiMS 2 ; V 2 O 5 ; LiV 2 O 5 ; LiQO 2 ; LiNiVO 4 ; Li (3-f) T′ 2 (PO 4 ) 3 (where 0 ⁇ f ⁇ 2); and LiFePO 4 .
- A may be selected from the group consisting of nickel (Ni), cobalt (Co), manganese (Mn), and a combination thereof
- D′ may be selected from aluminum (Al), Ni, Co, manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), a rare-earth element, and a combination thereof
- E may be selected from the group consisting of oxygen (O), fluorine (F), sulfur (S), phosphorus (P), and a combination thereof
- G may be selected from the group consisting of Co, Mn, and a combination thereof
- J may be selected from the group consisting of F, S, P, and a combination thereof
- L may be a transition metal or an element of a lanthanum group selected from the group consisting of Mg, calcium (Ca), Sr, barium (Ba), radium (Ra), scandium (Sc),yttrium (Y), titanium (Ti), zir
- the negative electrode active material may include a carbon-based material, a silicon-based material, or a silicon-carbon-based composite.
- the carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof.
- the crystalline carbon may be amorphous, plate-like, flake-like, spherical, or fibrous graphite, such as natural graphite or artificial graphite, and the amorphous carbon may include soft carbon (low-temperature calcined carbon), hard carbon (hard carbon), mesophase pitch carbide, calcined coke, and the like.
- the silicon-based material may include a silicon particle, a silicon alloy particle, or/and a silicon nanowire.
- the silicon-based material may include silicon particles, and an average particle diameter thereof may be in a range of 50 nm to 150 nm.
- the silicon-carbon-based composite may be a composite in which silicon nanoparticles are disposed on a carbon-based compound, a composite in which silicon particles are included on a surface and inside a carbon-based compound, or a composite in which silicon particles are coated with a carbon-based compound to be included inside a carbon-based compound.
- the carbon-based compound of the silicon-carbon-based composite may be graphite, graphene, graphene oxide, or a combination thereof,
- the negative electrode active material may include an active material obtained by dispersing silicon nanoparticles having an average particle of about 200 nm or less on the carbon-based compound particles and the coating them with carbon, an active material including silicon particles on and inside graphite, or the like.
- the silicon nanoparticles may have an average particle diameter in a range of 50 nm to 150 nm.
- the silicon-carbon-based composite may have an average particle diameter in a range of, for example, 1 ⁇ m to 20 ⁇ m.
- the lithium battery including the negative electrode active material may have further improved initial efficiency, capacity, and lifespan characteristics.
- the lithium battery may be prepared by the following method.
- a positive electrode is prepared.
- a positive electrode may be, for example, prepared according to the following method, but the preparation method is not necessarily limited thereto and may be adjusted to required conditions.
- a positive electrode active material composition may be prepared by mixing the aforementioned positive electrode active material, a conductive material, a binder, and a solvent.
- the prepared positive electrode active material composition may be directly coated and dried on an aluminum current collector to form a positive electrode plate provided with a positive electrode active material layer.
- a film obtained by casting the positive electrode active material composition on a separate support and separating it from the support may be laminated on an aluminum current collector to prepare a positive electrode plate on which the positive electrode active material layer is formed.
- Examples of the conductive material may be; carbon black, graphite particulates, natural graphite, artificial graphite, acetylene black, Ketjen black, carbon fibers; carbon nanotubes; metallic powder, metallic fiber, or metallic tube of copper, nickel, aluminum, silver, and the like; and a conductive polymer such as a polyphenylene derivative.
- a conductive polymer such as a polyphenylene derivative.
- binder examples include a vinylidene fluorideihexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE), a mixture of the aforementioned polymers, a styrene butadiene-rubber polymer, and the like, and examples of the solvent are N-methyl pyrrolidone (NMP), acetone, water, and the like.
- NMP N-methyl pyrrolidone
- acetone water, and the like.
- embodiments are not limited thereto, and any binder and solvent available in the art may be used.
- pores may be formed inside an electrode plate.
- the amounts of the positive electrode active material, the conductive material, the binder, and the solvent used in the positive electrode may be at levels general for use in a lithium battery. Depending on the use and configuration of the lithium battery, one or more of the conductive material, the binder, and the solvent may be omitted.
- the positive electrode active material may further include, in addition to the aforementioned positive electrode active material, a positive electrode active material described below.
- the positive electrode active material may be a lithium-containing metal oxide, and any material available in the art may be used.
- at least one composite oxide of lithium and a metal selected from Co, Mn, Ni, and a combination thereof may be used; and a specific example thereof may be a compound represented by one of the following formulae: Li a A 1-b B′ b D′ 2 (where 0.90 ⁇ a ⁇ 1 and 0 ⁇ b ⁇ 0.5); Li a E 1-b B′ b O 2-c D′ c (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiE 2-b B′ b O 4-c D′ c (where 0 ⁇ b ⁇ 0.5 and 0 ⁇ c ⁇ 0 .
- Li a Ni 1-b-c Co b B′ c D′ a (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0 . 05 , and 0 ⁇ 2); Li a Ni 1-b-c Co b B′ c O 2- ⁇ F′ 2 (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-b-c Mn b B′ c D′ ⁇ (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-b-c Mn b B′ c O 2- ⁇ F′ ⁇ (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-b-c Mn b B′ c O 2- ⁇ F′ ⁇ (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li
- the positive electrode active material may include LiCoO 2 , LiMn g O 2g (where g is 1 or 2), LiNi 1-g-k Co g Al k O 2 (where 0 ⁇ g ⁇ 1 and 0 ⁇ k ⁇ 0.5), LiNi 1-g-k Co g Mn k O 2 (0 ⁇ g ⁇ 0.5 0 ⁇ k ⁇ 0.5), or LiFePO 4 .
- a compound in which a coating layer is additionally provided on the surface of the aforementioned compound may be also used, and a mixture of the aforementioned compound and a compound additionally provided with a coating layer may be also used.
- the coating layer additionally provided on the surface of the aforementioned compound may include, for example, a coating element compound, such as an oxide of a coating element, a hydroxide of a coating element, oxyhydroxide of a coating element, oxycarbonate of a coating element, or hydroxycarbonate of a coating element.
- the compound constituting the coating layer may be amorphous or crystalline.
- the coating element included in the coating layer may be Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof.
- a method of forming the coating layer may be selected within a range that does not adversely affect the physical properties of the positive electrode active material.
- the coating method may be, for example, spray coating, dipping method, or the like. A detailed description of the coating method will be omitted because it may be well understood by those in the art.
- a negative electrode is prepared as follows.
- the negative electrode may be, for example; prepared in the same manner as in the positive electrode; except that the aforementioned negative electrode active material is used instead of the positive electrode active material.
- the substantially same conductive material, binder, and solvent as those used in the positive electrode preparation may be used.
- a negative electrode active material, a conductive material, a binder, and a solvent may be mixed to prepare a negative electrode active material composition.
- the negative electrode active material composition may be then directly coated on a copper current collector to prepare a negative electrode plate.
- a negative electrode active material film obtained by casting the negative electrode active material composition on a separate support and separating it from the support may be laminated on a copper current collector to prepare a negative electrode plate.
- the negative electrode active material any suitable negative electrode active material other than the aforementioned negative electrode active material and available in the art for a lithium battery may be used.
- the negative electrode active material may include at least one selected from lithium metal, a metal alloyable with lithium, a transition metal oxide, a non-transition metal oxide, and a carbon-based material.
- Examples of the metal alloyable with lithium are Si, Sn, Al, Ge, lead (Pb), Bi, Sb), a Si-Y′ alloy (where Y′ is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, and Y′ is not Si), and a Sn-Y′ alloy (wherein Y′ is an alkali metal, an alkaline earth-metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, and Y′ is not Sn).
- the element Y′ may be, for example, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
- the transition metal oxide may include, for example, a lithium titanium oxide, a vanadium oxide, a lithium vanadium oxide, and the like.
- the non-transition metal oxide may be, for example, SnO 2 , SiOx (where 0 ⁇ x ⁇ 2), and the like.
- the carbon-based material may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof.
- the crystalline carbon may be, for example, amorphous, plate-like, flake-like, spherical, or fibrous graphite, such as natural graphite or artificial graphite.
- the amorphous carbon may be, for example, soft carbon (carbon sintered at a low temperature) or hard carbon, mesophase pitch carbide, sintered coke, and the like.
- the amounts of the negative electrode active material, the conductive material, the binder, and the solvent may be at levels general for use in a lithium battery. Depending on the use and configuration of the lithium battery, one or more of the conductive material, the binder, and the solvent may be omitted.
- the separator may be any suitable separator commonly used in a lithium secondary battery.
- a material having low resistance to movement of ions in an electrolyte and excellent electrolyte wettability may be used.
- the separator may be selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and a combination thereof, and may be in any form of a non-woven fabric or a woven fabric.
- PTFE polytetrafluoroethylene
- a rollable separator including polyethylene, polypropylene, or the like may be used for a lithium ion battery, and a separator with excellent impregnation with an electrolyte may be used for a lithium ion polymer battery.
- the separator may be prepared by the following method.
- a separator composition may be prepared by mixing a polymer resin, a filler, and a solvent. Then, the separator composition may be directly coated on an electrode, and then dried to form a separator. Alternatively, the separator composition may be cast on a support, and then dried to form a separator film. The film may be then separated from the support and laminated on an electrode to form a separator.
- the polymer used in the preparation of the separator is not particularly limited, and any material available as the binder for an electrode plate may be used.
- a vinylidene fluoride/hexafluoropropylene copolymer, PVDF, polyacrylonitrile, polymethylmethacrylate, or a mixture thereof may be used.
- the electrolyte may further include, in addition to the aforementioned electrolyte, an organic solid electrolyte or/and an inorganic solid electrolyte.
- a polyethylene derivative a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, a polyester sulfide, polyvinyl alcohol, polyfluorinated vinylidene, or the Ike may be used.
- the solid electrolyte may be a boron oxide, a lithium oxynitride, or the like, but is not limited thereto. Any suitable solid electrolyte available in the art may be used.
- the inorganic solid electrolyte may be, for example, formed on the negative electrode by a method such as sputtering or the like, or a separate solid electrolyte sheet may laminated on the negative electrode.
- a lithium battery 1 includes a positive electrode 3 , a negative electrode 2 , and a composite separator 4 .
- the positive electrode 3 , the negative electrode 2 , and the composite separator 4 may be wound or folded to be accommodated in a battery case 5 .
- the battery case 5 may be filled with an electrolyte, and sealed with a cap assembly 6 , thereby completing the manufacture of the lithium battery 1 .
- the battery case 5 may be cylindrical, but the shape of the battery case 5 is not necessarily limited thereto.
- the battery case 5 may be a square-type, a thin-film type, or the like.
- the pouch-type lithium battery may include at least one battery assembly.
- the separator 4 may be disposed between the positive electrode 3 and the negative electrode 2 to form a battery assembly.
- the battery assembly may be laminated as a bi-cell structure, impregnated with an organic electrolyte, and accommodated and sealed in a pouch to complete the manufacture of a pouch-type lithium battery.
- Multiple battery assemblies are stacked to form a battery pack, and the battery pack may be used in all types of devices requiring high capacity and high output,
- the pouch-type lithium battery may be used in a laptop computer, a smart phone, an electronic vehicle, or the like.
- the lithium battery may be used in, for example, an electric vehicle (EV).
- EV electric vehicle
- the lithium battery may be used in a hybrid vehicle, such as a plug-in hybrid electric vehicle (PHEV).
- PHEV plug-in hybrid electric vehicle
- the lithium battery may be applicable to the fields requiring high-power storage.
- the lithium battery may be used in a electric bicycle, a power tool, or the like.
- a and b of the expression “Ca-Cb” refer to the number of carbon atoms of a specific functional group. That is, the functional group may include a to b carbon atoms.
- the term “C1-C4 alkyl group” refers to an alkyl group having 1 to 4 carbon atoms, and examples thereof are CH 3 —, CH 3 CH 2 —, CH 3 CH 2 CH 2 —, (CH 3 ) 2 CH—, CH 3 CH 2 CH 2 CH 2 —, CH 3 CH 2 CH(CH 3 )—, and (CH 3 ) 3 C—.
- radicals may include mono-radical or di-radical, depending on the context.
- substituent when a substituent requires two linkages to the rest of the molecule, the substituent should be understood as a diradical.
- a substituent specified for an alkyl group requiring two linkages includes a diradical, such as —CH 2 , —CH 2 CH 2 , —CH 2 CH(CH 3 )CH 2 —, and the like.
- radicals such as “alkylene” clearly indicates that the radical is a diradical.
- alkyl croup or “alkylene croup” refers to a branched or unbranched aliphatic hydrocarbon group. In an embodiment, the alkyl group may be substituted or unsubstituted.
- alkyl group examples are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like, but embodiments are not limited thereto. Each of these substituents may be selectively substituted or unsubstituted.
- the alkyl group may include 1 to 6 carbon atoms.
- Examples of the C1-C6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, hexyl, and the like, but embodiments are not limited thereto.
- cycloalkyl group refers to a fully saturated carbocyclic ring or ring system.
- the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.
- alkenyl group refers to a hydrocarbon group having at least one carbon-carbon double bond and 2 to 20 carbon atoms, and examples thereof are an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like, but embodiments are not limited thereto.
- the alkenyl group may be substituted or unsubstituted.
- the alkenyl group may include 2 to 40 carbon atoms.
- alkynyl group refers to a hydrocarbon group including 2 to 20 carbon atoms and at least one carbon-carbon triple bond, and examples thereof are an ethyny group, a 1-propynyl group, a 1-butynyl group. a 2-butynyl group, and the like. However, embodiments are not limited thereto.
- the alkynyl group may be substituted or unsubstituted.
- the alkynyl group may include 2 to 40 carbon atoms.
- aromatic refers to a ring or a ring system having a conjugated pi electron system, and examples thereof are a carbocyclic aromatic groups (e.g., a phenyl group) and a heterocyclic aromatic group (e.g., pyridine).
- the term includes a monocyclic or fused polycyclic ring (i.e., a ring that shares adjacent pairs of atoms) as long as the entire ring system is aromatic.
- aryl group refers to an aromatic ring or ring system in which the ring backbone includes only carbon atoms (i.e., two or more fused rings sharing two adjacent carbon atoms).
- the aryl group is a ring system, each ring in the system is aromatic.
- the aryl group may be a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a naphthacenyl group, or the like, but embodiments are not limited thereto.
- the aryl group may be substituted or unsubstituted.
- heteroaryl group refers to an aromatic ring system having one ring or multiple fused rings, wherein at least one ring atom is a hetero atom that is not carbon.
- a fused ring system one or more heteroatoms can be present in only one ring.
- the heteroatom may include oxygen, sulfur, and nitrogen, but is not necessarily limited thereto.
- the heteroaryl group may be a furanyl group, a thienyl group, an imidazolyl group, a quinazolinyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a pyridinyl group, a pyrrolyl group, an oxazolyl group, an indolyl group, or the like, but embodiments are not limited thereto.
- aralkyl group refers to an aryl group, such as a C7-C14 aralkyl group, connected as a substituent via an alkylene group, and examples thereof are a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, or a naphthyl alkyl group, but are not limited thereto.
- the alkylene group refers to a lower alkylene group (i.e., a C1-C4 alkylene group).
- cycloalkenyl group refers to a carbocyclic ring or ring system having at least one double bond, and is a ring system not having an aromatic ring.
- the cycloalkenyl group may be a cyclohexenyl group.
- heterocyclic group refers to a non-aromatic ring or ring system having at least one hetero atom in the ring skeleton.
- halogen refers to a stable element belonging to Group 17 of the Periodic Table of Elements, and for example, may be fluorine, chlorine, bromine or iodine, and particularly may be fluorine and/or chlorine.
- substituents are derived by exchanging at least one hydrogen with other atoms or a functional group in an unsubstituted mother group.
- the functional group is considered substituted with at least one substitute selected from a C1-C40 alkyl group, a C2-C40 alkenyl group, a C3-C40 cycloalkyl group, a C3-C40 cycloalkenyl group, a c1-C40 alkyl group, and a C7-C40 aryl group.
- a functional group is described as being “selectively substituted”, the functional group is considered substituted with the aforementioned substituent.
- a compound of Formula 5 was synthesized as follows.
- a compound of Formula 13 was synthesized as follows.
- Example 1 0.25 wt % of Compound Formula 5 and 5 wt % of FEC
- 1.2 M LiPF 6 was added to a solvent in which ethylene carbonate (EC), propylene carbonate (PC), ethyl propionate (EP), and propyl propionate (PP) were mixed at a volume ratio of 2:1:4:3. Then, 5 wt % of fluoroethylene carbonate (FEC) and 0.25 wt % of the compound of Formula 5 synthesized according to Synthesis Example 1 were added to the mixed solvent to prepare an electrolyte.
- EC ethylene carbonate
- PC propylene carbonate
- EP ethyl propionate
- PP propyl propionate
- Example 2 0.5 wt % of Compound of Formula 5
- An electrolyte was prepared in the same manner as in Example 1, except that 0.5 wt % of the compound of Formula 5 synthesized according to Synthesis Example 1 was added to the mixed solvent.
- Example 3 1 wt % of Compound of Formula 5
- An electrolyte was prepared in the same manner as in Example 1, except that 1 wt % of the compound of Formula 5 synthesized according to Synthesis Example 1 was added to the mixed solvent.
- An electrolyte was prepared in the same manner as in Example 1, except that 2 wt % of the compound of Formula 5 synthesized according to Synthesis Example 1 was added to the mixed solvent.
- LiPF6 1.2 M LiPF6 was added to a solvent in which EC, PC, EP, and PP were mixed at a volume ratio of 2:1:4:3 to prepare an electrolyte.
- An electrolyte was prepared in the same manner as in Example 1, except that 1 wt % of the compound of Formula 13 synthesized according to Synthesis Example 2 was added to the mixed solvent.
- An electrolyte was prepared in the same manner as in Example 1, except that 2 wt % of the compound of Formula 13 synthesized according to Synthesis Example 2 was added to the mixed solvent.
- 98 wt % of artificial graphite, 1 wt % of styrene-butadiene rubber (SBR), and 1 wt % of carboxymethyl cellulose (CMC) were mixed, added to distilled water, and then stirred by using a mechanical stirrer for 60 minutes to prepare a slurry for a negative active material slurry.
- the prepared slurry was applied to a thickness of about 60 ⁇ m on a 10 pm-thick copper current collector by using a doctor blade, dried in a hot-air dryer at 100° C. for 0.5 hour, dried again for 4 hours in a vacuum condition at 120° C., and then roll-pressed to prepare a negative electrode.
- LiCoO 2 (LCO) LiCoO 2
- 0.5 wt % of artificial graphite powder as a conductive material 0.8 wt % of ketjen black, 0.2 wt % of acrylonitrile rubber, and 1.5 wt % of polyvinylidene fluoride (PVdF) were mixed, added to N-methyl-2-pyrrolidone, and then stirred by using a mechanical stirrer for 30 minutes to prepare a slurry for a positive electrode active material.
- the prepared slurry was applied to a thickness of about 60 pm on a 20 pm-thick copper current collector by using a doctor blade, dried in a hot-air dryer at 100° C. for 0.5 hour, dried again for 4 hours in a vacuum condition at 120° C., and then roll-pressed to prepare a positive electrode,
- a 14 ⁇ m-thick polyethylene separator on which ceramic was coated on a positive electrode was used, and for use as an electrolyte, the electrolyte prepared according to Example 1 was used, to prepared a cylindrical-type lithium secondary battery.
- Lithium secondary batteries were prepared in the same manner as in Example 5, except that the electrolytes prepared according to Examples 2 to 4 were used respectively instead of the electrolyte prepared according to Example 1.
- Lithium secondary batteries were prepared in the same manner as in Example 5, except that the electrolytes prepared according to Comparative Examples 1 to 3 were used respectively instead of the electrolyte prepared according to Example 1.
- Each of the lithium secondary batteries prepared in Examples 5 to 8 and Comparative Examples 4 to 6 was charged with a constant current of 0.2 C rate at 25° C. until a voltage reached 4.4 voltage (V) (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.4 V in a constant voltage mode. Subsequently, the lithium secondary batteries were each discharged with a constant current of 0.2 C rate until the voltage reached 3.0 V (vs. Li) (formation step).
- Each of the lithium secondary batteries was charged with a constant current of 0.2 C rate at 25° C. until a voltage reached 4.4 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.4 V in a constant voltage mode. Subsequently, after stored for 4 hours at 25° C. and ⁇ 10° C., respectively, three cells that were discharged at 25° C. and ⁇ 10° C. with a constant current of 0.2 C rate until a voltage reached 3.4 V (vs. Li) were prepared. For each of the three cells, discharge capacity for each temperature (25° C. and ⁇ 10° C.) was measured. The results of evaluation are shown in Table 1. The discharge capacity ratio (%) at a low temperature ( ⁇ 10° C.) is defined by Equation 1:
- Discharge Capacity Ratio (%) at Low Temperature ( ⁇ 10° C.) [Discharge Capacity at ⁇ 10° C./Charge Capacity at 25° C.] ⁇ 100
- the lithium secondary batteries of Examples 5 to 8 include an additive having a structure in which silyl aroups substituted with an alkyl group (e.g., a methyl group) and an alkenyl group (e.g., an ethenyl group) are symmetrical at the center of phosphoric acid substituted with a halogen atom (e.g., fluorine) in the electrolyte,
- the lithium secondary batteries of Examples 5 to 8 had improved discharge capacity (ratio) at a low temperature ( ⁇ 10° C.) compared to the lithium secondary battery of Comparative Example 4 (in which an electrolyte was not used in the electrolyte).
- the lithium secondary batteries of Examples 5 to 8 had improved discharge capacity (ratio) at a low temperature ( ⁇ 10° C.) compared to the lithium secondary batteries prepared according to Comparative Examples 5 and 6.
- the additive used in the electrolyte of the lithium secondary battery of each of Examples 5 to 8 forms a cathode electrolyte interphase (CEI) film having low impedance characteristics on a surface of the positive electrode, and then forms a solid electrolyte interphase (SEI) having a high silyl group concentration on a surface of the negative electrode. Accordingly, the lithium secondary battery including the electrolyte including the additive seemed to have improved discharge capacity (ratio) at a low temperature ( ⁇ 10° C.).
- Each of the lithium secondary batteries prepared in Examples 5 to 8 and Comparative Examples 4 to 6 was charged with a constant current of 1.0 C rate at 45° C. until a voltage reached 4.47 V (vs, Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.47 V in a constant voltage mode. Subsequently, the lithium secondary batteries were each discharged with a constant current of 1.0 C rate until the voltage reached 3.0 V (vs. Li), Such a charging/discharging cycle was repeated 100 times. After every one charge/discharge cycle in all the charge/discharge cycles, there was a 10-minute pause time. The results of evaluation are shown in Table
- Equation 2 The capacity retention ratio at the 100 th cycle is defined by Equation 2:
- Capacity retention ratio (%) (discharge capacity in 100 th cycle/discharge capacity in 1 st cycle) ⁇ 100 Equation 2
- the lithium secondary batteries of Examples 5 to 8 had high capacity retention ratio of about 0.4% to about 7% at 45° C., compared to the lithium secondary batteries of Comparative Examples 4 (in which an additive was not used in the electrolyte) and Comparative Examples 5 and 6 (in which 1 wt % and 2 wt % of Compound 1 of Formula 13 were used as an additive in the electrolyte).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
An electrolyte for a lithium battery and a lithium battery including the same are provided. The electrolyte for a lithium battery may include: a lithium salt; a non-aqueous organic solvent; and an additive including a compound represented by Formula 1.
Description
- The present disclosure relates to an electrolyte for a lithium battery and a lithium battery including the same.
- Lithium batteries have energy density per unit weight that is three times higher than that of a lead-acid battery, a nickel-cadmium battery, a nickel-hydrogen battery, a nickel-zinc battery, and the like in the art, and can be charged at high speed.
- Since a lithium secondary battery operates at a high driving voltage, an aqueous electrolyte solution having high reactivity with lithium cannot be used. Instead, an organic electrolyte solution is generally in a lithium secondary battery. The organic electrolyte solution is prepared by dissolving a lithium salt in a non-aqueous organic solvent. For use as the non-aqueous organic solvent, a material stable at a high voltage and having high ionic conductivity and dielectric permittivity and low viscosity is preferable.
- However, use of the organic electrolyte solution as an electrolyte for a lithium secondary battery may cause degradation in capacity and lifespan characteristics of the lithium secondary battery due to side reactions between an electrolyte and a negative electrode/positive electrode.
- In order to compensate for this point, an additive is used in the electrolyte for a lithium secondary battery. However, additives used so far do not provide sufficient capacity and lifespan characteristics of a battery over a wide temperature range between a low temperature below zero and a high temperature.
- Thus, there is still a need for an electrolyte for a lithium battery and a lithium battery including the same, the electrolyte capable of providing sufficient capacity and lifespan characteristics of a battery over a wide temperature range between a low temperature below zero and a high temperature.
- One aspect is to provide an electrolyte for a lithium battery, including a novel electrolyte additive.
- Another aspect is to provide a lithium battery including the electrolyte.
- According to an aspect of the disclosure, an electrolyte for a lithium battery includes:
-
- a lithium salt;
- a non-aqueous organic solvent; and
- an additive including a compound represented by Formula 1;
-
- wherein, in Formula 1,
- X1 and X2 may each independently be —O— or —N—;
- Y may be a halogen atom or a substituted or unsubstituted C1-C1O alkoxy group; and
- R1, R2, R3, R4, R5, and R6 may each independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C6-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group.
- The compound represented by Formula 1 may be represented by Formula 2:
-
- wherein, in Formula 2,
- Y′ may be a halogen atom or a substituted or unsubstituted C1-C10 alkoxy group; and
- R′1, R′2, R′3, R′4, R′5, and R′6 may each independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C6-C50 alkylaryl group.
- The compound represented by Formula 1 may be represented by Formula 3:
-
- wherein, in Formula 3,
- Y″ may be a halogen atom; and
- Ra, Rb, Rc, Rd, and Rf may each independently be an unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group substituted with a halogen atom, an unsubstituted C2-C10 alkenyl group, a C2-C10 alkenyl group substituted with a halogen atom, an unsubstituted C6-C50 alkylaryl group, or a C6-C50 alkylaryl group substituted with a halogen atom.
- The compound represented by Formula 1 may be represented by Formulae 4 to
- The amount of the additive may be in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte.
- The electrolyte may further include a cyclic carbonate-based compound, and
- The cyclic carbonate-based compound may be selected from: fluoroethylene carbonate (FEC); FFC substituted with at least one substituent selected from a halogen atom, a cyano group (CN), and a nitro group (NO2); vinyl ethylene carbonate (VEC); VEC substituted with at least one substituent selected from a halogen atom, CN, and NO2; vinylene carbonate (VC); and VC substituted with at least one substituent selected from a halogen atom, CN, and NO2.
- The electrolyte may further include at least one selected from a sultone-based compound, a nitride-based compound, and a cyanide-based compound.
- The sultone-based compound may be: sultone; or propane sultone substituted with at least one substituent selected from a halogen atom, a cyano group, a nitro group, a trifluoromethanesulfonic group, a pentafluoroethanesulfonyl group (SO2C2F5), a pentafluorophenyl group (C6F5), a methanesulfonyl group (SO2CF3), a phenylsulfonyl group (SO2Ph), and a methylester group (COOCH3).
- The nitride-based compound may be succinonitrile,
- The cyanide-based compound may be 1,3,6-hexane tri-cyanide (HTCN) or 1,2,6-(HTCN).
- The amount of the sultone-based compound, the nitride-based compound, or the cyanide-based compound may be in a range of 0.01 wt % to 5 wt % based on the total weight of the electrolyte.
- The lithium salt may include at least one selected from LiPF6, LiBF4, LiSbF6, LiASF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2)(where and 2≤x≤20 and 2≤y≤20), LiCl, and Lil.
- The non-aqueous organic solvent may include at least one selected from ethylene carbonate (EC), propylene carbonate (PC), ethylmethyl carbonate (EMC), methylpropyl carbonate, ethylpropyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, vinylethylene carbonate (VEC), butylene carbonate, ethyl propionate (EP), propyl propionate (PP), ethyl butylate, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, gamma-valerolactone, gamma-butyrolactone, and tetrahydrofuran.
- According to another aspect, a lithium battery includes:
-
- a positive electrode including a positive electrode active material;
- a negative electrode including a negative electrode active material; and
- an electrolyte disposed between the positive electrolyte and the negative electrode.
- The negative electrode active material may include a carbon-based material, a silicon-based material, or a silicon-carbon-based composite.
- The negative electrode active material may include amorphous, plate-like, flake-like, spherical, or fibrous graphite, such as natural graphite or artificial graphite.
- The lithium battery may further include a separator between the positive electrode and the negative electrode.
- The electrolyte for a lithium battery according to one aspect includes an additive including a compound represented by Formula 1. A lithium battery including the electrolyte may have improved discharge capacity (ratio) and lifespan characteristics at a low temperature (−10° C.) below zero and a high temperature (45° C.).
-
FIG. 1 is a schematic view of a lithium battery according to an embodiment. - Hereinafter, an electrolyte for a lithium battery and a lithium battery including the same will be described in detail with reference to embodiments and drawings of the present disclosure. These examples are only presented by way of example to explain the present disclosure in more detail, and it will be apparent to those skilled in the art that the scope of the present disclosure is not limited by these examples.
- Unless otherwise defined, all technical and scientific terms used in the present specification have the same meaning as commonly understood by those skilled in the art to which the disclosure belongs to. In case of conflict, the present specification including definitions is considered in priority.
- Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described herein. An expression used in the singular encompasses the expression of the plural, unless it has a clearly different meaning in the context.
- It will be further understood that the terms “comprises” or “includes” when used in the present specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
- The term “a combination thereof” as used herein means a mixture or combination of one or more of the aforementioned elements.
- The term “and/or” as used herein is meant to include any and all combinations of one or more of the items listed in relation thereto. The term “or” as used herein means “and/or”. The expression “at least one” or “one or more” used in front of components in the present specification is meant to supplement a list of all components means, and does not imply to supplement individual components of the description.
- In the drawings, thicknesses may be magnified or exaggerated to clearly illustrate various layers and regions. Like reference numbers may refer to like elements throughout the drawings and the following description. It will be understood that when one element, layer, film, section, sheet, etc. is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. Although the terms “first,” “second,” etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element.
- An electrolyte for a lithium battery according to an embodiment may include: a lithium salt; a non-aqueous organic solvent; and an additive including a compound represented by Formula 1:
- wherein, in
Formula 1, - X1 and X2 may each independently be —O— or —N—;
- Y may be a halogen atom or a substituted or unsubstituted C1-C10 alkoxy group; and
- R1, R2, R3, R4, R5, and R6 may each independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C6-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group.
- The electrolyte for a lithium battery according to an embodiment may include, as an additive, the compound represented by
Formula 1. The compound may be an additive having a symmetric structure in which silyl groups are located on both sides of a center at which a phosphorus (P) element and an oxygen (O) element form a double bond (—P═O). A lithium battery using the electrolyte that includes the additive may have improved discharge capacity (ratio) and lifespan characteristics at a low temperature (−10° C.) below zero and a high temperature (45° C.). - The reason for improving the discharge capacity (ratio) at a low temperature below zero (−10° C.) and a high temperature (45° C.) and lifespan characteristics of a lithium battery by adding the compound represented by
Formula 1 as an additive to the electrolyte for a lithium battery will be described in detail below. However, the description below is to help understanding the present disclosure, and are not for purposes of limiting the scope of the present disclosure thereto. - When the compound represented by
Formula 1 is included as an additive in the electrolyte, a cathode electrolyte interphase (CEI) film may be formed on a surface of a positive electrode. The CEI film strongly interacts with metal ions of a metal oxide included in a positive electrode active material so that the reaction center at the interface between the electrolyte and a positive electrode can be completely capped to be deactivated. In addition, the CEI film may prevent generation of by-products, such as gas or/and HF, by preventing oxidation of a solvent included in the electrolyte, and may also prevent the elusion of metal ions of a metal oxide included in a positive electrode active material. Accordingly, in a lithium battery including the electrolyte, resistance at the interface between the electrolyte and a positive electrode is lowered so that lithium ion conductivity may be improved while a low-temperature discharge voltage may increase. As a result, the lithium battery may have improved cycle stability and rate performance. - In addition, the additive may have a symmetric structure in which silyl groups are located on both sides of a center at which a phosphorus (P) element and an oxygen (O) element form a double bond (—P═O). Such an additive may have a high concentration of silyl groups compared to an additive having a structure in which a silyl group is located only on one side. On a surface of a negative electrode, a highly polar and stable solid electrolyte interphase (SEI) film may be formed. Resistance at the interface between the electrolyte and a negative electrode may be lowered so that lithium ion conductivity may be improved while a low-temperature discharge voltage may increase.
- For example, the compound represented by Formula 1 may include a compound represented by Formula 2:
- wherein, in
Formula 2, - Y′ may be a halogen atom or a substituted or unsubstituted C1-C16 alkoxy group; and
- R′1, R′2, R′3, R′4, R′5, and R′6 may each independently be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C6-C50 alkylaryl group.
- For example, the compound represented by Formula 1 may include a compound represented by Formula 3:
- wherein, in
Formula 3, - Y″ may be a halogen atom; and
- Ra, Rb, Rc, Rd, Re, and Rf may each independently be an unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group substituted with a halogen atom, an unsubstituted C2-C10 alkenyl group, a C2-C10 alkenyl group substituted with a halogen atom, an unsubstituted C6-C50 alkylaryl group, or a C6-C50 alkylaryl group substituted with a halogen atom.
- For example, the compound represented by Formula 1 may include a compound represented by Formulae 4 to 12:
- The amount of the additive may be in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte. For example, the amount of the additive may be, based on the total weight of the electrolyte, in a range of 0.01 wt % to 9 wt %, 0.01 wt % to 8 wt %, 0.01 wt % to 7 wt %, 0.01 wt % to 6 wt %, 0.01 wt % to 5 wt %, 0.01 wt % to 4 wt %, 0.01 wt % to 3 wt %, or 0.01 wt % to 2 wt %. By including the electrolyte within the ranges above, the lithium battery may have improved discharge capacity (ratio) and lifespan characteristics at a low temperature (−10° C.) below zero and a high temperature (45° C.).
- The electrolyte may further include a cyclic carbonate-based compound, and the cyclic carbonate-based compound may be selected from: fluoroethylene carbonate (FEC); FEC substituted with at least one substituent selected from a halogen atom, a cyano group (CN), and a nitro group (NO2); vinylethylene carbonate (VEC); VEC substituted with at least one substituent selected from a halogen atom, CN, and NO2; vinylene carbonate (VC); and VC substituted with at least one substituent selected from a halogen atom, CN, and NO2.
- The amount of the cyclic carbonate-based compound may be in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte. For example, the amount of the cyclic carbonate-based compound may be in a range of 0.1 wt % to 10 wt % or 0.5 wt % to 10 wt %, based on the total weight of the electrolyte.
- An SEI film formed by a reaction between the cyclic carbonate-based compound and either of a negative electrode active material or a negative electrode surface may have more flexible characteristics. Accordingly, the lifespan characteristics of the lithium battery may be further improved.
- The electrolyte may further include at least one selected from a sultone-based compound, a nitride-based compound, and a cyanide-based compound, wherein the sultone-based compound may include: propane sultone; or propane sultone substituted at least one substituent selected from a halogen atom, a cyano group, a nitro group, a trifluoromethane sulfonyl group, a pentafluoroethane sulfonyl group (SO2C2F5), a pentafluorophenyl group (C6F5), a methane sulfonyl group (SO2CF3), a phenyl sulfonyl group (SO2Ph), and a methyl ester group(COOCH3), the nitride-based compound may include succinonitrile, and the cyanide-based compound may include 1, 3, 6-hexane tri-cyanide (HTCN) or 1, 2, 6-HTCN.
- The amount of the sultone-based compound, the nitride-based compound, or the cyanide-based compound may be in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte. For example, the amount of the sultone-based compound, the nitride-based compound, or the cyanide-based compound may be in a range of 0.1 wt % to 10 wt %, 0.5 wt % to 10 wt %, or 1 wt % to 10 wt %, based on the total weight of the electrolyte, When the sultone-based compound orland the nitride-based compound is further added to the electrolyte, the interfacial resistance of a negative electrode may be lowered and the thermal stability is improved, and thus the lifespan characteristics of lithium battery at a high temperature may be further improved. When the cyanide-based compound is further added to the electrolyte, the thickness of the lithium battery may be reduced, and accordingly, the stability of the battery against thermal shock may be improved.
- The lithium salt may include at least one selected from LiPF6, LiBF4, LiSbF6, LiASF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2)(where and 2≤x≤20 and 2≤y≤20), LiCl, and Lil. In the electrolyte, the concentration of the lithium salt may be in a range of 0.01 M to 2.0 M, but is not necessarily limited thereto. An appropriate concentration may be used as needed. Within the concentration ranges above, the battery performance may be further improved.
- The non-aqueous organic solvent may include at least one selected from ethylene carbonate (EC), propylene carbonate (PC), ethylmethyl carbonate (EMC), methylpropyl carbonate, ethylpropyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, vinylethylene carbonate (VEC), butylene carbonate, ethyl propionate (EP), propyl propionate (PP), ethyl butylate, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, gamma-valerolactone, gamma-butyrolactone, and tetrahydrofuran. However, examples are not limited thereto, and any non-aqueous organic solvent available in the art may be used.
- The electrolyte may be in a liquid state or a gel state. A lithium battery according to another embodiment may include: a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; and the electrolyte disposed between the positive electrode and the negative electrode. The shape of the lithium battery is not particularly limited, and the lithium battery, such as a lithium ion battery, a lithium ion polymer battery, a lithium sulfur battery, and the like, may also include a lithium primary battery.
- By including the electrolyte, the lithium battery may have improved discharge capacity (ratio) and lifespan characteristics at a low temperature (−10° C.) below zero and a high temperature (45° C.).
- For example, the positive electrode active material may be selected from compounds represented by the following formulae: LibA1-bD′bE2 (where 0.90≤a≤1.8 and 0≤b≤0.5); LiaG1-bD′bO2-cEc (where 0.90≤a≤1.8, 0≤b≤0.5, and 0≤c≤0.05); LiG2-bD′bO4-cEc (where 0≤b≤0.5 and 0≤c≤0.05); LiaNi1-b-cCobD′cEα (where 0.90≤a ≤1.8, 0≤b≤0.5, 0≤c≤0.05, and 0<α≤2); LiaNi1-b-cCobD′cO2-αJα (where 0.90≤a≤1.8, 0≤b≤0.5. 0≤c≤0.05, and 0<α<2); LiaNi1-b-cCobD′cO2-αJ2 (where 0.90≤a≤1.8, 0≤b ≤0.5, 0≤c≤0.05, and 0<α<2); LiaNi1-b-cMnbD′cEα (where 0.90≤a≤1.8, 0≤b≤0.5, 0 ≤c≤0.05, and 0<α≤2); LiaNi1-b-cMnbD′cO2-αJα (where 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, and 0<α<2); LiaNi1-b-cMnbD′cO2-αJ2 (where 0.90≤a≤1.8, 0≤b≤≤0.5, 0≤c≤0.05, and 0<α<2); LiaNibGcLdO2 (where 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, and 0.0001≤d≤0.2); LiaNibGcO2 (where 0.90≤a≤1.8, 0≤b≤0.9, and 0≤c≤0.5); LiaNibCocMndLeO2 (where 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, and 0.001≤e≤0.2); LiaNibCocMndO2 (where 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, and 0≤d≤0.5); LiaNiLbO2 (where 0.90≤a≤1.8 and 0.001≤b≤0.2); LiaCoLbO2 (where 0.90≤a≤1.8 and 0.001≤b≤0.2); LiaMnLbO2 (where 0.90≤a≤1.8 and 0.001≤b≤0.2); LiaMn2LbO4 a≤1.8 and a≤1.8 and 0.001≤b≤0.2); LiaMn2O4 (where 0.90≤a≤1.8); MO2; MS2; LiMS2; V2O5; LiV2O5; LiQO2; LiNiVO4; Li(3-f)T′2(PO4)3 (where 0≤f≤2); and LiFePO4.
- In the formulae above, A may be selected from the group consisting of nickel (Ni), cobalt (Co), manganese (Mn), and a combination thereof, D′ may be selected from aluminum (Al), Ni, Co, manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), a rare-earth element, and a combination thereof, E may be selected from the group consisting of oxygen (O), fluorine (F), sulfur (S), phosphorus (P), and a combination thereof, G may be selected from the group consisting of Co, Mn, and a combination thereof, J may be selected from the group consisting of F, S, P, and a combination thereof, L may be a transition metal or an element of a lanthanum group selected from the group consisting of Mg, calcium (Ca), Sr, barium (Ba), radium (Ra), scandium (Sc),yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), rutherfordium (Rf), V, niobium (Nb), tantalum (Ta), dubnium (Db), Cr, molybdenum (Mo), tungsten (W), seaborgium (Sg), technetium (Tc), rhenium (Re), bohrium (Bh), Fe, ruthenium (Ru), osmium (Os), hassium (Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), boron (B), Al, gallium (Ga), indium (In), thallium (TI), silicon (Si), germanium (Ge), tin (Sn), P, arsenic (As), antimony (Sb), bismuth (Bi), S, selenium (Se), tellurium (Te), polonium (Po), Mn, lanthanum (La), cerium (Ce), and a combination thereof, M may be selected from the group consisting of Ti, Mo, Mn, and a combination thereof, Q may be selected from the group consisting of Cr, V, Fe, Sc, Ti, Y, and a combination thereof, and T″ may be selected from the group consisting of V, Cr, Mn, Co, Ni, Cu, and a combination thereof. In detail, the positive electrode active material may be LiCoO2.
- The negative electrode active material may include a carbon-based material, a silicon-based material, or a silicon-carbon-based composite.
- The carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof. The crystalline carbon may be amorphous, plate-like, flake-like, spherical, or fibrous graphite, such as natural graphite or artificial graphite, and the amorphous carbon may include soft carbon (low-temperature calcined carbon), hard carbon (hard carbon), mesophase pitch carbide, calcined coke, and the like.
- The silicon-based material may include a silicon particle, a silicon alloy particle, or/and a silicon nanowire. For example, the silicon-based material may include silicon particles, and an average particle diameter thereof may be in a range of 50 nm to 150 nm.
- The silicon-carbon-based composite may be a composite in which silicon nanoparticles are disposed on a carbon-based compound, a composite in which silicon particles are included on a surface and inside a carbon-based compound, or a composite in which silicon particles are coated with a carbon-based compound to be included inside a carbon-based compound. The carbon-based compound of the silicon-carbon-based composite may be graphite, graphene, graphene oxide, or a combination thereof,
- For example, the negative electrode active material may include an active material obtained by dispersing silicon nanoparticles having an average particle of about 200 nm or less on the carbon-based compound particles and the coating them with carbon, an active material including silicon particles on and inside graphite, or the like. The silicon nanoparticles may have an average particle diameter in a range of 50 nm to 150 nm. The silicon-carbon-based composite may have an average particle diameter in a range of, for example, 1 μm to 20 μm. The lithium battery including the negative electrode active material may have further improved initial efficiency, capacity, and lifespan characteristics.
- The lithium battery may be prepared by the following method.
- First, a positive electrode is prepared.
- A positive electrode may be, for example, prepared according to the following method, but the preparation method is not necessarily limited thereto and may be adjusted to required conditions.
- First, a positive electrode active material composition may be prepared by mixing the aforementioned positive electrode active material, a conductive material, a binder, and a solvent. The prepared positive electrode active material composition may be directly coated and dried on an aluminum current collector to form a positive electrode plate provided with a positive electrode active material layer. Alternatively, a film obtained by casting the positive electrode active material composition on a separate support and separating it from the support may be laminated on an aluminum current collector to prepare a positive electrode plate on which the positive electrode active material layer is formed.
- Examples of the conductive material may be; carbon black, graphite particulates, natural graphite, artificial graphite, acetylene black, Ketjen black, carbon fibers; carbon nanotubes; metallic powder, metallic fiber, or metallic tube of copper, nickel, aluminum, silver, and the like; and a conductive polymer such as a polyphenylene derivative. However, embodiments are not limited thereto, and any suitable conductive material available in the art may be used.
- Examples of the binder are a vinylidene fluorideihexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE), a mixture of the aforementioned polymers, a styrene butadiene-rubber polymer, and the like, and examples of the solvent are N-methyl pyrrolidone (NMP), acetone, water, and the like. However, embodiments are not limited thereto, and any binder and solvent available in the art may be used.
- By further adding a plasticizer or a pore former to the positive electrode active material composition, pores may be formed inside an electrode plate.
- The amounts of the positive electrode active material, the conductive material, the binder, and the solvent used in the positive electrode may be at levels general for use in a lithium battery. Depending on the use and configuration of the lithium battery, one or more of the conductive material, the binder, and the solvent may be omitted. The positive electrode active material may further include, in addition to the aforementioned positive electrode active material, a positive electrode active material described below.
- The positive electrode active material may be a lithium-containing metal oxide, and any material available in the art may be used. For example; at least one composite oxide of lithium and a metal selected from Co, Mn, Ni, and a combination thereof may be used; and a specific example thereof may be a compound represented by one of the following formulae: LiaA1-bB′bD′2 (where 0.90≤a≤1 and 0≤b≤0.5); LiaE1-bB′bO2-cD′c (where 0.90≤a≤1, 0≤b≤0.5, and 0≤c≤0.05); LiE2-bB′bO4-cD′c (where 0≤b≤0.5 and 0≤c÷0.05); LiaNi1-b-cCobB′cD′a (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, and 0<α≤2); LiaNi1-b-cCobB′cO2-αF′2 (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, and 0<α<2); LiaNi1-b-cMnbB′cD′α (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, and 0<α≤2); LiaNi1-b-cMnbB′cO2-αF′α (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, and 0<α<2); LiaNi1-b-cMnbB′cO2-αF′2 (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, and 0<α<2); LiaNibEcGdO2 (where 0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, and 0.001≤d≤0.1.); LiaNibCocMndGeO2 (where 0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.05, 0≤d≤0.5, and 0.001≤e≤0.1); LiaNiGbO2 (where 0.90≤a≤1 and 0.001≤b≤0.1); LiaCoGbO2 (where 0.90≤a≤1 and 0.001≤b≤0,1); LiaMnGbO2 (where 0.90≤a≤1 and 0.001≤b≤0.1); LiaMn2GbO4 where 0.90≤a≤1 and 0.001≤b≤0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiNiVO4; Li(3-f)J2(PO4)3 (where 0≤f≤2); Li(3-f)Fe2(PO4)3 (where 0≤f≤2); and LiFePO4.
- In the formulae above representing the compound, A may be Ni, Co, Mn, or a combination thereof; a may be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D may be O, F, S, P, or a combination thereof; E may be Co, Mn, or a combination thereof; F′ may be F, S, P, or a combination thereof; G may be Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q may be Ti, Mo, Mn, or a combination thereof; I′ may be Cr, V, Fe, Sc, Y, or a combination thereof; and J may be V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
- For example, the positive electrode active material may include LiCoO2, LiMngO2g (where g is 1 or 2), LiNi1-g-kCogAlkO2 (where 0<g<1 and 0<k≤0.5), LiNi1-g-kCogMnkO2(0≤g≤0.5 0≤k≤0.5), or LiFePO4.
- A compound in which a coating layer is additionally provided on the surface of the aforementioned compound may be also used, and a mixture of the aforementioned compound and a compound additionally provided with a coating layer may be also used. The coating layer additionally provided on the surface of the aforementioned compound may include, for example, a coating element compound, such as an oxide of a coating element, a hydroxide of a coating element, oxyhydroxide of a coating element, oxycarbonate of a coating element, or hydroxycarbonate of a coating element. The compound constituting the coating layer may be amorphous or crystalline. The coating element included in the coating layer may be Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof. A method of forming the coating layer may be selected within a range that does not adversely affect the physical properties of the positive electrode active material. The coating method may be, for example, spray coating, dipping method, or the like. A detailed description of the coating method will be omitted because it may be well understood by those in the art.
- Next, a negative electrode is prepared as follows. The negative electrode may be, for example; prepared in the same manner as in the positive electrode; except that the aforementioned negative electrode active material is used instead of the positive electrode active material. In addition, in the negative electrode active material composition, the substantially same conductive material, binder, and solvent as those used in the positive electrode preparation may be used.
- For example, a negative electrode active material, a conductive material, a binder, and a solvent may be mixed to prepare a negative electrode active material composition. The negative electrode active material composition may be then directly coated on a copper current collector to prepare a negative electrode plate. Alternatively, a negative electrode active material film obtained by casting the negative electrode active material composition on a separate support and separating it from the support may be laminated on a copper current collector to prepare a negative electrode plate.
- As the negative electrode active material, any suitable negative electrode active material other than the aforementioned negative electrode active material and available in the art for a lithium battery may be used. For example, the negative electrode active material may include at least one selected from lithium metal, a metal alloyable with lithium, a transition metal oxide, a non-transition metal oxide, and a carbon-based material.
- Examples of the metal alloyable with lithium are Si, Sn, Al, Ge, lead (Pb), Bi, Sb), a Si-Y′ alloy (where Y′ is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, and Y′ is not Si), and a Sn-Y′ alloy (wherein Y′ is an alkali metal, an alkaline earth-metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, and Y′ is not Sn). The element Y′ may be, for example, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
- The transition metal oxide may include, for example, a lithium titanium oxide, a vanadium oxide, a lithium vanadium oxide, and the like.
- The non-transition metal oxide may be, for example, SnO2, SiOx (where 0<x<2), and the like.
- The carbon-based material may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof. The crystalline carbon may be, for example, amorphous, plate-like, flake-like, spherical, or fibrous graphite, such as natural graphite or artificial graphite. The amorphous carbon may be, for example, soft carbon (carbon sintered at a low temperature) or hard carbon, mesophase pitch carbide, sintered coke, and the like.
- The amounts of the negative electrode active material, the conductive material, the binder, and the solvent may be at levels general for use in a lithium battery. Depending on the use and configuration of the lithium battery, one or more of the conductive material, the binder, and the solvent may be omitted.
- Next, a separator to be disposed between the positive electrode and the negative electrode is prepared.
- The separator may be any suitable separator commonly used in a lithium secondary battery. For use as the separator, a material having low resistance to movement of ions in an electrolyte and excellent electrolyte wettability may be used. For example, the separator may be selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and a combination thereof, and may be in any form of a non-woven fabric or a woven fabric. For example, a rollable separator including polyethylene, polypropylene, or the like may be used for a lithium ion battery, and a separator with excellent impregnation with an electrolyte may be used for a lithium ion polymer battery. For example, the separator may be prepared by the following method.
- A separator composition may be prepared by mixing a polymer resin, a filler, and a solvent. Then, the separator composition may be directly coated on an electrode, and then dried to form a separator. Alternatively, the separator composition may be cast on a support, and then dried to form a separator film. The film may be then separated from the support and laminated on an electrode to form a separator.
- The polymer used in the preparation of the separator is not particularly limited, and any material available as the binder for an electrode plate may be used. For example, a vinylidene fluoride/hexafluoropropylene copolymer, PVDF, polyacrylonitrile, polymethylmethacrylate, or a mixture thereof may be used.
- Next, the aforementioned electrolyte is prepared.
- The electrolyte may further include, in addition to the aforementioned electrolyte, an organic solid electrolyte or/and an inorganic solid electrolyte.
- For example, as the organic solid electrolyte, a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, a polyester sulfide, polyvinyl alcohol, polyfluorinated vinylidene, or the Ike may be used.
- For example, the solid electrolyte may be a boron oxide, a lithium oxynitride, or the like, but is not limited thereto. Any suitable solid electrolyte available in the art may be used. The inorganic solid electrolyte may be, for example, formed on the negative electrode by a method such as sputtering or the like, or a separate solid electrolyte sheet may laminated on the negative electrode.
- As shown in
FIG. 1 , alithium battery 1 includes apositive electrode 3, anegative electrode 2, and a composite separator 4. Thepositive electrode 3, thenegative electrode 2, and the composite separator 4 may be wound or folded to be accommodated in abattery case 5. Then, thebattery case 5 may be filled with an electrolyte, and sealed with acap assembly 6, thereby completing the manufacture of thelithium battery 1. Thebattery case 5 may be cylindrical, but the shape of thebattery case 5 is not necessarily limited thereto. For example, thebattery case 5 may be a square-type, a thin-film type, or the like. - For example, the pouch-type lithium battery may include at least one battery assembly. The separator 4 may be disposed between the
positive electrode 3 and thenegative electrode 2 to form a battery assembly. The battery assembly may be laminated as a bi-cell structure, impregnated with an organic electrolyte, and accommodated and sealed in a pouch to complete the manufacture of a pouch-type lithium battery. Multiple battery assemblies are stacked to form a battery pack, and the battery pack may be used in all types of devices requiring high capacity and high output, For example, the pouch-type lithium battery may be used in a laptop computer, a smart phone, an electronic vehicle, or the like. - Since the lithium battery has excellent lifespan characteristics and excellent high-rate characteristics, the lithium battery may be used in, for example, an electric vehicle (EV). For example, the lithium battery may be used in a hybrid vehicle, such as a plug-in hybrid electric vehicle (PHEV). In addition, the lithium battery may be applicable to the fields requiring high-power storage. For example, the lithium battery may be used in a electric bicycle, a power tool, or the like.
- In the present specification, a and b of the expression “Ca-Cb” refer to the number of carbon atoms of a specific functional group. That is, the functional group may include a to b carbon atoms, For example, the term “C1-C4 alkyl group” refers to an alkyl group having 1 to 4 carbon atoms, and examples thereof are CH3—, CH3CH2—, CH3CH2CH2—, (CH3)2CH—, CH3CH2CH2CH2—, CH3CH2CH(CH3)—, and (CH3)3C—.
- The nomenclature for a particular radical may include mono-radical or di-radical, depending on the context. For example, when a substituent requires two linkages to the rest of the molecule, the substituent should be understood as a diradical. For example, a substituent specified for an alkyl group requiring two linkages includes a diradical, such as —CH2, —CH2CH2, —CH2CH(CH3)CH2—, and the like. The nomenclature for other radicals, such as “alkylene” clearly indicates that the radical is a diradical.
- In this specification, the term “alkyl croup” or “alkylene croup” refers to a branched or unbranched aliphatic hydrocarbon group. In an embodiment, the alkyl group may be substituted or unsubstituted. Examples of the alkyl group are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like, but embodiments are not limited thereto. Each of these substituents may be selectively substituted or unsubstituted. In an embodiment, the alkyl group may include 1 to 6 carbon atoms. Examples of the C1-C6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, hexyl, and the like, but embodiments are not limited thereto.
- In the present specification, the term “cycloalkyl group” refers to a fully saturated carbocyclic ring or ring system. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.
- In this specification, the term “alkenyl group” refers to a hydrocarbon group having at least one carbon-carbon double bond and 2 to 20 carbon atoms, and examples thereof are an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like, but embodiments are not limited thereto. In an embodiment, the alkenyl group may be substituted or unsubstituted. In an embodiment, the alkenyl group may include 2 to 40 carbon atoms.
- In the present specification, the term “alkynyl group” refers to a hydrocarbon group including 2 to 20 carbon atoms and at least one carbon-carbon triple bond, and examples thereof are an ethyny group, a 1-propynyl group, a 1-butynyl group. a 2-butynyl group, and the like. However, embodiments are not limited thereto. In an embodiment, the alkynyl group may be substituted or unsubstituted. In an embodiment, the alkynyl group may include 2 to 40 carbon atoms.
- In the present specification, the term “aromatic” refers to a ring or a ring system having a conjugated pi electron system, and examples thereof are a carbocyclic aromatic groups (e.g., a phenyl group) and a heterocyclic aromatic group (e.g., pyridine). The term includes a monocyclic or fused polycyclic ring (i.e., a ring that shares adjacent pairs of atoms) as long as the entire ring system is aromatic.
- In the present specification, the term “aryl group” refers to an aromatic ring or ring system in which the ring backbone includes only carbon atoms (i.e., two or more fused rings sharing two adjacent carbon atoms). When the aryl group is a ring system, each ring in the system is aromatic. For example, the aryl group may be a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a naphthacenyl group, or the like, but embodiments are not limited thereto. The aryl group may be substituted or unsubstituted.
- In the present specification, the term “heteroaryl group” refers to an aromatic ring system having one ring or multiple fused rings, wherein at least one ring atom is a hetero atom that is not carbon. In a fused ring system, one or more heteroatoms can be present in only one ring. For example, the heteroatom may include oxygen, sulfur, and nitrogen, but is not necessarily limited thereto. For example, the heteroaryl group may be a furanyl group, a thienyl group, an imidazolyl group, a quinazolinyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a pyridinyl group, a pyrrolyl group, an oxazolyl group, an indolyl group, or the like, but embodiments are not limited thereto.
- In the present specification, the term “aralkyl group” or “alkylaryl group” refers to an aryl group, such as a C7-C14 aralkyl group, connected as a substituent via an alkylene group, and examples thereof are a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, or a naphthyl alkyl group, but are not limited thereto. In an embodiment, the alkylene group refers to a lower alkylene group (i.e., a C1-C4 alkylene group).
- In the present specification, the term “cycloalkenyl group” refers to a carbocyclic ring or ring system having at least one double bond, and is a ring system not having an aromatic ring. For example, the cycloalkenyl group may be a cyclohexenyl group.
- In the present specification, the term “heterocyclic group” refers to a non-aromatic ring or ring system having at least one hetero atom in the ring skeleton.
- In this specification, the term “halogen” refers to a stable element belonging to Group 17 of the Periodic Table of Elements, and for example, may be fluorine, chlorine, bromine or iodine, and particularly may be fluorine and/or chlorine.
- In the present specification, substituents are derived by exchanging at least one hydrogen with other atoms or a functional group in an unsubstituted mother group. Unless otherwise stated, when a function group is considered “substituted”, the functional group is considered substituted with at least one substitute selected from a C1-C40 alkyl group, a C2-C40 alkenyl group, a C3-C40 cycloalkyl group, a C3-C40 cycloalkenyl group, a c1-C40 alkyl group, and a C7-C40 aryl group. When a functional group is described as being “selectively substituted”, the functional group is considered substituted with the aforementioned substituent.
- The disclosure is in greater details through Examples and Comparative Examples below. However, the following embodiments are for illustrative purpose only and shall not be construed as limiting the scope of the disclosure.
- A compound of
Formula 5 was synthesized as follows. - Sodium fluorophosphate (9.96 g, 0.07 mol) was added to chloro(dimethyl)vinyl silane (25.05 g, 021 mol) at 25° C. (room temperature). DMF (35 ml) was added to the reaction mixture, and then stirred at 25° C. for 20 hours. Subsequently, the white precipitate was filtered, and the filtrate was purified by fractional distillation to obtain colorless oil (9.5 g, 50%).
- 1H NMR (400 MHz, CDCl3) δ=0.37 (s, 12 H), 5.85-5.91 (dd, 2 H), 6.06-6.19 (m, 4 H).
- 19F NMR (376.17 MHz, CDCl3) δ=−71.96 (d, 1JFP=935 Hz).
- 31P NMR (161.83 MHz, CDCl3) δ=−26.0 (d, 1JFP=935 Hz).
- A compound of Formula 13 was synthesized as follows.
- Diethyl phosphorochloridate (4,66 g, 0.027 mol) was slowly added to N,N-bis(trimethylsilyl)methylamine (5.26 g, 0.03 mol) at 25° C. (room temperature). The reaction mixture was stirred at 25° C. for 24 hours. After distillation, the resulting product was obtained as colorless liquid (4.56 g, 70%).
- 1H NMR (400 MHz, CDCl3) δ=0.20 (s, 9 H), 1.27 (t, 6 H), 2.55 (d, 3 H), 3.89-4.01 (m, 4 H).
- 31P NMR (161.83 MHz, CDCl3) δ=−11.96.
- 1.2 M LiPF6 was added to a solvent in which ethylene carbonate (EC), propylene carbonate (PC), ethyl propionate (EP), and propyl propionate (PP) were mixed at a volume ratio of 2:1:4:3. Then, 5 wt % of fluoroethylene carbonate (FEC) and 0.25 wt % of the compound of
Formula 5 synthesized according to Synthesis Example 1 were added to the mixed solvent to prepare an electrolyte. - An electrolyte was prepared in the same manner as in Example 1, except that 0.5 wt % of the compound of
Formula 5 synthesized according to Synthesis Example 1 was added to the mixed solvent. - An electrolyte was prepared in the same manner as in Example 1, except that 1 wt % of the compound of
Formula 5 synthesized according to Synthesis Example 1 was added to the mixed solvent. - An electrolyte was prepared in the same manner as in Example 1, except that 2 wt % of the compound of
Formula 5 synthesized according to Synthesis Example 1 was added to the mixed solvent. - 1.2 M LiPF6 was added to a solvent in which EC, PC, EP, and PP were mixed at a volume ratio of 2:1:4:3 to prepare an electrolyte.
- An electrolyte was prepared in the same manner as in Example 1, except that 1 wt % of the compound of Formula 13 synthesized according to Synthesis Example 2 was added to the mixed solvent.
- An electrolyte was prepared in the same manner as in Example 1, except that 2 wt % of the compound of Formula 13 synthesized according to Synthesis Example 2 was added to the mixed solvent.
- 98 wt % of artificial graphite, 1 wt % of styrene-butadiene rubber (SBR), and 1 wt % of carboxymethyl cellulose (CMC) were mixed, added to distilled water, and then stirred by using a mechanical stirrer for 60 minutes to prepare a slurry for a negative active material slurry. The prepared slurry was applied to a thickness of about 60 μm on a 10 pm-thick copper current collector by using a doctor blade, dried in a hot-air dryer at 100° C. for 0.5 hour, dried again for 4 hours in a vacuum condition at 120° C., and then roll-pressed to prepare a negative electrode.
- 97 wt % of LiCoO2(LCO), 0.5 wt % of artificial graphite powder as a conductive material, 0.8 wt % of ketjen black, 0.2 wt % of acrylonitrile rubber, and 1.5 wt % of polyvinylidene fluoride (PVdF) were mixed, added to N-methyl-2-pyrrolidone, and then stirred by using a mechanical stirrer for 30 minutes to prepare a slurry for a positive electrode active material. The prepared slurry was applied to a thickness of about 60 pm on a 20 pm-thick copper current collector by using a doctor blade, dried in a hot-air dryer at 100° C. for 0.5 hour, dried again for 4 hours in a vacuum condition at 120° C., and then roll-pressed to prepare a positive electrode,
- For use as a separator, a 14 μm-thick polyethylene separator on which ceramic was coated on a positive electrode was used, and for use as an electrolyte, the electrolyte prepared according to Example 1 was used, to prepared a cylindrical-type lithium secondary battery.
- Lithium secondary batteries were prepared in the same manner as in Example 5, except that the electrolytes prepared according to Examples 2 to 4 were used respectively instead of the electrolyte prepared according to Example 1.
- Lithium secondary batteries were prepared in the same manner as in Example 5, except that the electrolytes prepared according to Comparative Examples 1 to 3 were used respectively instead of the electrolyte prepared according to Example 1.
- Evaluation Example 1: Discharge Capacity (Ratio) at Low Temperature (−10° C.)
- Each of the lithium secondary batteries prepared in Examples 5 to 8 and Comparative Examples 4 to 6 was charged with a constant current of 0.2 C rate at 25° C. until a voltage reached 4.4 voltage (V) (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.4 V in a constant voltage mode. Subsequently, the lithium secondary batteries were each discharged with a constant current of 0.2 C rate until the voltage reached 3.0 V (vs. Li) (formation step).
- Each of the lithium secondary batteries was charged with a constant current of 0.2 C rate at 25° C. until a voltage reached 4.4 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.4 V in a constant voltage mode. Subsequently, after stored for 4 hours at 25° C. and −10° C., respectively, three cells that were discharged at 25° C. and −10° C. with a constant current of 0.2 C rate until a voltage reached 3.4 V (vs. Li) were prepared. For each of the three cells, discharge capacity for each temperature (25° C. and −10° C.) was measured. The results of evaluation are shown in Table 1. The discharge capacity ratio (%) at a low temperature (−10° C.) is defined by Equation 1:
-
-
TABLE 1 Discharge Discharge Discharge Cell capacity (mAh) capacity (mAh) capacity ratio Division No. at 25° C. at −10° C. (%) at −10° C. Example 5 1 5.00 3.43 68.5 2 5.00 3.55 71.0 3 5.00 3.43 68.5 Example 6 1 5.03 3.56 70.8 2 4.99 3.53 70.7 3 5.02 3.56 70.9 Example 7 1 5.00 3.56 71.2 2 5.02 3.60 71.6 3 5.03 3.60 71.5 Example 8 1 5.02 3.83 76.2 2 5.01 3.81 76.2 3 4.98 3.63 72.9 Comparative 1 4.99 3.09 62.0 Example 4 2 5.00 3.16 63.3 3 4.99 3.11 62.3 Comparative 1 5.05 3.29 65.3 Example 5 2 5.01 3.06 61.1 3 5.02 3.15 62.7 Comparative 1 5.12 3.36 65.6 Example 6 2 4.97 3.23 64.9 3 4.98 3.25 65.3 - Referring to Table 1 the discharge capacity of each of the lithium secondary batteries of Examples 5 to 8 at a low temperature (−10° C.) was higher than that of each of the lithium secondary batteries of Comparative Examples 4 to 6 (in which an additive was not used in an electrolyte, and 1 wt % and 2 wt % of the
Compound 1 of Formula 13 were used) by about 3% to about 15%. The lithium secondary batteries of Examples 5 to 8 include an additive having a structure in which silyl aroups substituted with an alkyl group (e.g., a methyl group) and an alkenyl group (e.g., an ethenyl group) are symmetrical at the center of phosphoric acid substituted with a halogen atom (e.g., fluorine) in the electrolyte, The lithium secondary batteries of Examples 5 to 8 had improved discharge capacity (ratio) at a low temperature (−10° C.) compared to the lithium secondary battery of Comparative Example 4 (in which an electrolyte was not used in the electrolyte). In addition, it was confirmed that the lithium secondary batteries of Examples 5 to 8 had improved discharge capacity (ratio) at a low temperature (−10° C.) compared to the lithium secondary batteries prepared according to Comparative Examples 5 and 6. - The additive used in the electrolyte of the lithium secondary battery of each of Examples 5 to 8 forms a cathode electrolyte interphase (CEI) film having low impedance characteristics on a surface of the positive electrode, and then forms a solid electrolyte interphase (SEI) having a high silyl group concentration on a surface of the negative electrode. Accordingly, the lithium secondary battery including the electrolyte including the additive seemed to have improved discharge capacity (ratio) at a low temperature (−10° C.).
- Each of the lithium secondary batteries prepared in Examples 5 to 8 and Comparative Examples 4 to 6 was charged with a constant current of 1.0 C rate at 45° C. until a voltage reached 4.47 V (vs, Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.47 V in a constant voltage mode. Subsequently, the lithium secondary batteries were each discharged with a constant current of 1.0 C rate until the voltage reached 3.0 V (vs. Li), Such a charging/discharging cycle was repeated 100 times. After every one charge/discharge cycle in all the charge/discharge cycles, there was a 10-minute pause time. The results of evaluation are shown in Table
- 2. The capacity retention ratio at the 100th cycle is defined by Equation 2:
-
Capacity retention ratio (%)=(discharge capacity in 100th cycle/discharge capacity in 1st cycle)×100Equation 2 -
TABLE 2 Capacity Initial discharge Discharge capacity retention Division capacity (mAh) at 100 cycle (mAh) ratio (%) Example 5 4.92 4.15 84.3 Example 6 4.95 4.25 85.8 Example 7 5.03 4.48 89.1 Example 8 4.91 4.17 85.0 Comparative 4.97 4.09 82.4 Example 4 Comparative 4.96 4.20 84.6 Example 5 Comparative 4.99 4.12 82.6 Example 6 - Referring to Table 2, the lithium secondary batteries of Examples 5 to 8 had high capacity retention ratio of about 0.4% to about 7% at 45° C., compared to the lithium secondary batteries of Comparative Examples 4 (in which an additive was not used in the electrolyte) and Comparative Examples 5 and 6 (in which 1 wt % and 2 wt % of
Compound 1 of Formula 13 were used as an additive in the electrolyte).
Claims (10)
1. An electrolyte for a lithium battery comprising:
a lithium salt;
a non-aqueous organic solvent; and
an additive comprising a compound represented by Formula 1:
wherein, in Formula 1,
X1 and X2 are each independently —O— or —N—;
Y is a halogen atom or a substituted or unsubstituted C1-C10 alkoxy group; and
R1, R2, R3, R4, R5, and R6 are each independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C6-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group.
2. The electrolyte of claim 1 , wherein the compound represented by Formula 1 comprises a compound represented by Formula 2:
wherein, in Formula 2,
Y′ is a halogen atom or a substituted or unsubstituted C1-C10 alkoxy group; and
R′1, R′2, R′3, R′4, R′5, and R′6 are each independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C6-C50 alkylaryl group.
3. The electrolyte of claim 1 , wherein the compound represented by Formula 1 comprises a compound represented by Formula 3:
wherein, in Formula 3,
Y″ is a halogen atom; and
Ra, Rb, Rc, Rd, Re, and Rf are each independently an unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group substituted with a halogen atom, an unsubstituted C2-C10 alkenyl group, a C2-C10 alkenyl group substituted with a halogen atom, an unsubstituted C6-C50 alkylaryl group, or a C6-C50 alkylaryl group substituted with a halogen atom.
5. The electrolyte of claim 1 , wherein the amount of the additive is in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte.
6. The electrolyte of claim 1 , further comprising a cyclic carbonate-based compound,
wherein the cyclic carbonate-based compound is selected from: fluoroethylene carbonate (FEC); FFC substituted with at least one substituent selected from a halogen atom, a cyano group (CN), and a nitro group (NO2); vinylethylene carbonate (VEC); VEC substituted with at least one substituent selected from a halogen atom, CN, and NO2; vinylene carbonate (VC); and VC substituted with at least one substituent selected from a halogen atom, CN, and NO2.
7. The electrolyte of claim 6 , wherein the amount of the cyclic carbonate-based compound is in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte.
8. The electrolyte of claim 1 , further comprising at least one selected from a sultone-based compound, a nitride-based compound, and a cyanide-based compound,
wherein the sultone-based compound is: sultone; or propane sultone substituted with at least one substituent selected from a halogen atom, a cyano group, a nitro group, a trifluoromethanesulfonyl group, a pentafluoroethanesulfonyl group (SO2C2F5), a pentafluorophenyl group (C6F5), a methanesulfonyl group (SO2CF3), a phenylsulfonyl group (SO2Ph), and a methylester group (COOCH3),
the nitride-based compound is succinonitrile, and
the cyanide-based compound is 1,3,6-hexane tri-cyanide (HTCN) or 1,2,6-(HTCN).
9. The electrolyte of claim 8 , wherein the amount of the sultone-based compound, the nitride-based compound, or the cyanide-based compound is in a range of 0.01 wt % to 10 wt % based on the total weight of the electrolyte.
10. A lithium battery comprising:
a positive electrode comprising a positive electrode active material;
a negative electrode comprising a negative electrode active material; and
the electrolyte according to claim 1 disposed between the positive electrode and the negative electrode.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2021-0002216 | 2021-01-07 | ||
KR1020210002216A KR20220099852A (en) | 2021-01-07 | 2021-01-07 | Electrolyte for lithium battery, and lithium battery including the same |
PCT/KR2021/018481 WO2022149740A1 (en) | 2021-01-07 | 2021-12-07 | Electrolyte for lithium battery, and lithium battery comprising same |
Publications (1)
Publication Number | Publication Date |
---|---|
US20230268552A1 true US20230268552A1 (en) | 2023-08-24 |
Family
ID=82357212
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/003,717 Pending US20230268552A1 (en) | 2021-01-07 | 2021-12-07 | Electrolyte for lithium battery, and lithium battery comprising same |
Country Status (5)
Country | Link |
---|---|
US (1) | US20230268552A1 (en) |
EP (1) | EP4276966A1 (en) |
KR (1) | KR20220099852A (en) |
CN (1) | CN116648803A (en) |
WO (1) | WO2022149740A1 (en) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20150014185A (en) * | 2013-07-29 | 2015-02-06 | 주식회사 엘지화학 | Liquid Electrolyte for Secondary Battery and Lithium Secondary Battery Containing the Same |
JP2016196452A (en) * | 2015-04-02 | 2016-11-24 | 旭化成株式会社 | Compound, electrolyte additive, electrolyte, and lithium ion secondary battery |
CN109950620B (en) * | 2017-12-20 | 2021-05-14 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery |
WO2019220829A1 (en) * | 2018-05-14 | 2019-11-21 | ダイキン工業株式会社 | Electrolytic solution, electrochemical device, lithium-ion secondary battery, and module |
CN112625062B (en) * | 2020-12-17 | 2022-09-09 | 珠海冠宇电池股份有限公司 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
-
2021
- 2021-01-07 KR KR1020210002216A patent/KR20220099852A/en active Search and Examination
- 2021-12-07 US US18/003,717 patent/US20230268552A1/en active Pending
- 2021-12-07 WO PCT/KR2021/018481 patent/WO2022149740A1/en active Application Filing
- 2021-12-07 EP EP21917902.5A patent/EP4276966A1/en active Pending
- 2021-12-07 CN CN202180088465.5A patent/CN116648803A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP4276966A1 (en) | 2023-11-15 |
KR20220099852A (en) | 2022-07-14 |
WO2022149740A1 (en) | 2022-07-14 |
CN116648803A (en) | 2023-08-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11127978B2 (en) | Organic electrolytic solution and lithium battery including the same | |
US10320032B2 (en) | Organic electrolytic solution and lithium battery using the same | |
US11329318B2 (en) | Electrolyte additive for lithium secondary battery and lithium secondary battery including the same | |
US11114694B2 (en) | Lithium battery | |
KR20170018739A (en) | Electrolyte for lithium battery and Lithium battery including the electrolyte | |
US9748607B2 (en) | Electrolyte for lithium battery and lithium battery including the electrolyte | |
KR20140139906A (en) | Additive for electrolyte of lithium battery, organic electrolytic solution comprising the same and Lithium battery using the solution | |
US11239499B2 (en) | Additive, electrolyte for lithium secondary battery and lithium secondary battery including the same | |
US10923767B2 (en) | Organic electrolyte solution and lithium battery including organic electrolyte solution | |
US20220158224A1 (en) | Lithium secondary battery including electrolyte additive for lithium secondary battery | |
US11264645B2 (en) | Lithium battery | |
US20230268552A1 (en) | Electrolyte for lithium battery, and lithium battery comprising same | |
US11145900B2 (en) | Lithium battery | |
US11637322B2 (en) | Lithium battery | |
KR20190133659A (en) | Additive for electrolyte of lithium battery, organic electrolytic solution comprising the same and Lithium battery using the solution | |
US20180083317A1 (en) | Additive composition for lithium battery electrolyte, organic electrolyte including the same, and lithium battery including the additive composition | |
US20230318035A1 (en) | Electrolyte for lithium battery and lithium battery comprising same | |
US11264644B2 (en) | Lithium battery | |
US11251432B2 (en) | Lithium battery | |
US11936001B2 (en) | Electrolyte additive for lithium secondary battery and lithium secondary battery including the same | |
US20220407114A1 (en) | Organic electrolytic solution and lithium battery including the same | |
US11335952B2 (en) | Lithium battery | |
US20200266490A1 (en) | Lithium secondary battery including alkoxy phosphine-based additive | |
CN110931858A (en) | Lithium battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SAMSUNG SDI CO., LTD., KOREA, REPUBLIC OF Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TSAY, OLGA;PARK, HYEJIN;SHATUNOV, PAVEL;AND OTHERS;SIGNING DATES FROM 20221226 TO 20221227;REEL/FRAME:062331/0139 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |